DPP-based polymers are widely used in organic photovoltaics (OPV) and organic field-effect transistors (OFET) as the p-type materials. DPP with bithiophene (π-bridge) has already been proven to have excellent charge transport properties owing to an attractive S···O electrostatic interaction that induces π–π stacking. Therefore, we were performed Stille coupling reaction to combine these D–A building blocks to form the desired HTL. PD2FCT-29DPP (D1–A1–D1–A2) is a D–A alternating copolymer from the DPP (A2) and CPDT (D1) with fluorinated BT (A1). PD2FCT-29DPP-based devices achieve an FF of 70.0% and a PCE of 14.0%.